CN112457479A - Biodegradable transparent liquid polyester capable of being rapidly photocured with mercapto crosslinking agent, and preparation method and application thereof - Google Patents

Biodegradable transparent liquid polyester capable of being rapidly photocured with mercapto crosslinking agent, and preparation method and application thereof Download PDF

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CN112457479A
CN112457479A CN202011332994.9A CN202011332994A CN112457479A CN 112457479 A CN112457479 A CN 112457479A CN 202011332994 A CN202011332994 A CN 202011332994A CN 112457479 A CN112457479 A CN 112457479A
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transparent liquid
polyester
transparent
bdm
pmcl
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CN112457479B (en
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肖艳
郎美东
王照闯
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East China University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14—Macromolecular materials
    • A61L27/18—Macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones

Abstract

The invention discloses a biodegradable transparent liquid polyester capable of being rapidly photocured with a mercapto crosslinking agent, which has the following structure:
Figure DDA0002794572170000011
x + y is 10 to 100, and theoretically x ═ y. The invention also relates toDiscloses a transparent polyester photocuring mixed solution which is prepared from the biodegradable transparent liquid polyester and can be rapidly photocured. The transparent polyester photocuring mixed solution adopts liquid terminal alkynyl modified poly (4-methyl caprolactone) as a main material, has good biocompatibility and biodegradability of polycaprolactone, enables photocuring to be free of any solvent due to the normal-temperature liquid characteristic, achieves the zero VOC standard, is transparent, and can smoothly enable curing light to penetrate through.

Description

Biodegradable transparent liquid polyester capable of being rapidly photocured with mercapto crosslinking agent, and preparation method and application thereof
Technical Field
The invention belongs to the field of photocuring high polymer materials, and particularly relates to biodegradable transparent liquid polyester which is biodegradable, has good biocompatibility and can be rapidly photocured with a mercapto crosslinking agent, and a preparation method and application thereof.
Background
The photocuring material is a curing molding material developed by relying on a photocuring technology, and has very wide application in the fields of coatings, dentistry, adhesives, microelectronics and biomaterials due to a simple molding curing mode. With the issuance of sustainable development policies and the gradual shift of photocuring materials to high-value-added industries such as biomedicine and the like, the traditional acrylate and epoxy photosensitive resins cannot meet the requirements, so that biodegradable photocuring materials are widely concerned.
Biodegradable polymer materials are generally classified into two major types, i.e., natural degradable materials such as collagen, chitosan, sodium alginate, cellulose and starch, and synthetic materials such as polycaprolactone, polylactic acid, polyglycolic acid and polycarbonate. The degradable photocuring material generally modifies or functionalizes a degradable high polymer material, wherein the most common method is to modify carbon-carbon double bonds on the material to endow the material with a photocuring function, but the crosslinking of the double bonds usually generates free radicals and has certain cytotoxicity, and the crosslinking can be hindered by oxygen, so that the crosslinking rate is influenced, and the application in the deeper biomedical field is limited.
Among these materials, the material itself does not have fluidity due to its own characteristics such as crystallinity or high viscosity, and needs to be dissolved by an organic solvent for film-laying or mold-forming. According to the requirements of environmental protection law, the limitation on organic volatile compounds (VOC) in the photocuring material is more and more strict, the photocuring material gradually develops to low VOC or zero VOC, and the material which is dissolved by an organic solvent does not meet the environmental protection requirement. Therefore, there is a need to develop a biodegradable material that has good biocompatibility, has fluidity by itself (zero VOC), and can be rapidly photo-cured in air.
Disclosure of Invention
In order to overcome the technical problems of slow curing, high VOC, crosslinking toxicity, nondegradable property and the like of the traditional photocuring material, the invention aims to provide the biodegradable transparent liquid polyester which can be rapidly photocured with a mercapto crosslinking agent.
The second purpose of the invention is to provide a preparation method of the biodegradable transparent liquid polyester which can be rapidly photo-cured with a mercapto crosslinking agent.
The third purpose of the invention is to provide a transparent polyester photocuring mixed solution prepared by the biodegradable transparent liquid polyester.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the first aspect of the invention provides a biodegradable transparent liquid polyester capable of being rapidly photocured with a mercapto crosslinking agent, which has the following structure:
Figure BDA0002794572150000021
x + y is 10 to 100, and theoretically x ═ y.
Preferably, x + y is 10, theoretically x is 5; or x + y is 50, theoretically x is 25; or x + y 100, theoretically x y 50.
The second aspect of the present invention provides a preparation method of the biodegradable transparent liquid polyester capable of being rapidly photocured with a mercapto crosslinking agent, comprising the following steps:
the preparation method of the transparent liquid monomer 4-methyl caprolactone comprises the following steps:
dropwise adding a dichloromethane solution of 4-methylcyclohexanone into a dichloromethane solution of 3-chloroperoxybenzoic acid at a constant speed in an ice water bath, wherein the mass ratio of 4-methylcyclohexanone to 3-chloroperoxybenzoic acid is 1 (1.5-4) (preferably 1:2), and reacting at room temperature for 1-24 h after dropwise adding is finished to obtain a transparent liquid monomer 4-methylhexanolide;
in the second step, the preparation method of the transparent liquid polymer poly (4-methyl caprolactone) BDM-PMCL comprises the following steps:
under the protection of argon and under the anhydrous condition, 1, 4-Benzenedimethanol (BDM) with the molar ratio of 1 (10-200) and 4-methyl caprolactone (MeCL) prepared in the first step are uniformly mixed, and Sn (Oct) accounting for 0.5 wt% of the mass of the 4-methyl caprolactone prepared in the first step is added2Carrying out polymerization reaction for 1-24 h at the temperature of 120-140 ℃ to obtain a transparent liquid polymer poly (4-methyl caprolactone) BDM-PMCL;
thirdly, the preparation method of the transparent liquid BDM-PMCL-CDI comprises the following steps:
dissolving the transparent liquid polymer BDM-PMCL obtained in the second step into toluene, then respectively adding CDI and potassium hydroxide, wherein the mass ratio of the BDM-PMCL to the CDI to the potassium hydroxide is 20 (0.4-10): 1, and reacting for 1-24 h at the temperature of 50-70 ℃ to obtain the transparent liquid BDM-PMCL-CDI;
fourthly, the preparation method of the transparent liquid poly (4-methyl caprolactone) BDM-PMCL-yne with the end group of alkynyl comprises the following steps:
and (3) dissolving the transparent liquid BDM-PMCL-CDI prepared in the third step into toluene, adding 3-butine-1-alcohol and potassium hydroxide respectively for dissolving, wherein the mass ratio of the BDM-PMCL-CDI to the 3-butine-1-alcohol to the potassium hydroxide is 20 (0.1-3) to 1, and reacting at 50-70 ℃ for 1-24 hours to obtain transparent liquid polyester BDM-PMCL-yne.
The third aspect of the invention provides a transparent polyester photocuring mixed solution prepared from the biodegradable transparent liquid polyester, which is prepared from the following components: biodegradable transparent liquid polyester, a cross-linking agent containing sulfydryl and a photoinitiator; the mass ratio of the biodegradable transparent liquid polyester to the crosslinking agent containing sulfydryl is 10 (0.1-5), and the photoinitiator accounts for 1-3% of the total mass of the biodegradable transparent liquid polyester, the crosslinking agent containing sulfydryl and the photoinitiator.
The crosslinking agent containing sulfydryl is pentaerythritol tetra (3-mercaptopropionate).
The photoinitiator is 2,4, 6-trimethyl benzoyl phenyl ethyl phosphonate (TPO-L).
The fourth aspect of the invention provides a preparation method of the transparent polyester photocuring mixed solution, which comprises the following steps:
and (2) carrying out ultrasonic oscillation and uniform mixing on the transparent liquid polyester, a cross-linking agent containing sulfydryl and a photoinitiator to obtain a transparent polyester photocuring mixed solution, and irradiating for 30 s-5 min by using 405nm light to obtain the transparent polyester elastomer.
Due to the adoption of the technical scheme, the invention has the following advantages and beneficial effects:
transparent liquid 4-methyl caprolactone is used as a raw material, transparent liquid poly (4-methyl caprolactone) containing triple bonds is obtained through ring-opening polymerization and two-step end group modification, and is mixed with a liquid cross-linking agent (pentaerythritol tetrakis (3-mercaptopropionate)) and a liquid photoinitiator TPO-L to obtain a biodegradable transparent polyester photocuring mixed solution capable of being rapidly photocured, and the biodegradable transparent polyester elastomer can be obtained through crosslinking and curing at 405 nm.
The biodegradable transparent polyester photocuring mixed solution capable of being rapidly photocured adopts liquid terminal alkynyl modified poly (4-methyl caprolactone) as a main material, has good biocompatibility and biodegradability of polycaprolactone, enables photocuring to be free of any solvent due to the normal-temperature liquid characteristic, achieves the zero VOC standard, is transparent, can smoothly enable curing light to penetrate through, can rapidly realize curing and increase the curing thickness of the material, is green and environment-friendly in raw materials, and is simple and safe in curing steps. Secondly, the material is cured by utilizing thiol-alkyne click chemistry crosslinking, and has mild preparation conditions and simple process. The material has good light transmission performance, the cross-linked product is a transparent elastomer, the material has the characteristic similar to PDMS, and compared with the traditional double-bond cross-linking mode, the material has the advantages of high curing speed, no fear of oxygen inhibition, no biological toxicity and the like. And the normal-temperature liquid and quick photocuring characteristics of the material are very suitable for mold microstructure molding and serve as liquid ink for photocuring type 3D printing, the material is suitable for 3D printing of DLP, SLA and the like, a three-dimensional elastomer tissue engineering support can be printed, and a possibility is provided for soft tissue growth. The method has good application prospect in biomedical fields such as tissue engineering, soft materials and micro-channels and in aspects such as 3D printing.
Drawings
FIG. 1 is a drawing illustrating the first step of preparing 4-methylhexanolide in a biodegradable transparent liquid polyester capable of being rapidly photo-cured with thiol crosslinking agent prepared in example 1 of the present invention1H NMR spectrum.
FIG. 2 is a drawing illustrating a second step of preparing BDM-PMCL in biodegradable transparent liquid polyester which can be rapidly photo-cured with mercapto crosslinking agent prepared in example 1 of the present invention1H NMR spectrum.
FIG. 3 is a drawing illustrating BDM-PMCL-CDI prepared in the third step of biodegradable transparent liquid polyester capable of being rapidly photo-cured with mercapto crosslinking agent prepared in example 1 of the present invention1H NMR spectrum. x + y is 10, and theoretically x is 5.
FIG. 4 is a drawing illustrating BDM-PMCL-yne prepared in the fourth step of the biodegradable transparent liquid polyester prepared by the invention in example 1 and capable of being rapidly photo-cured with mercapto crosslinking agent1H NMR spectrum. x + y is 10, and theoretically x is 5.
FIG. 5 is a GPC chart of biodegradable transparent liquid polyester rapidly photo-curable with thiol crosslinking agent prepared in example 1 of the present invention.
FIG. 6 is a schematic view of a rheological test of a biodegradable transparent liquid polyester that can be rapidly photo-cured with a thiol crosslinking agent, prepared in example 1 of the present invention.
Fig. 7 is a schematic view of rapid curing of a transparent polyester photocuring mixture composed of biodegradable transparent liquid polyester prepared in example 1 of the present invention.
FIG. 8 is a schematic view of FT-IR spectrum of a transparent polyester photocuring mixture composed of biodegradable transparent liquid polyester prepared in example 1 of the present invention cured in air.
Fig. 9 is a schematic view of a cured transparent film of a transparent polyester photocuring mixture composed of biodegradable transparent liquid polyester prepared in example 1 of the present invention.
Fig. 10 is a schematic 3D printing diagram of a transparent polyester photocuring mixture composed of biodegradable transparent liquid polyester prepared in example 1 of the present invention.
FIG. 11 is a graph showing the in vitro degradation curve of the elastomer cured by the light-cured transparent polyester mixed solution composed of the biodegradable transparent liquid polyester prepared in example 1 of the present invention.
Fig. 12 is a schematic diagram showing cell proliferation of an elastomer after curing a transparent polyester photocuring mixed solution composed of biodegradable transparent liquid polyester prepared in example 1 of the present invention.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Example 1
A method for preparing biodegradable transparent liquid polyester capable of being rapidly photocured with mercapto crosslinking agent comprises the following steps:
step one, 4-methylcyclohexanone is used as a raw material, 3-chloroperoxybenzoic acid is oxidized to obtain transparent liquid monomer 4-methylhexalactone:
dissolving 60.00g of 4-methylcyclohexanone in 100ml of dichloromethane, dropwise adding the solution into 500ml of dichloromethane solution containing 120.00g of 3-chloroperoxybenzoic acid at a constant speed in an ice water bath, reacting at room temperature for 24 hours after the dropwise adding is finished, removing solids by suction filtration, washing the solution by saturated sodium thiosulfate, sodium bicarbonate and sodium chloride aqueous solution in sequence, and distilling under reduced pressure to obtain a transparent liquid monomer 4-methylhexalactone (MeCL). FIG. 1 is a drawing illustrating the first step of preparing 4-methylhexanolide in a biodegradable transparent liquid polyester capable of being rapidly photo-cured with thiol crosslinking agent prepared in example 1 of the present invention1H NMR spectrum.1H NMR(400MHz,CDCl3,TMS):δ＝4.32-4.14ppm(a,2H,-COOCH2-),2.73-2.57(e,2H,-CH2COO-),1.99-1.28(b,c,d,5H,-CHCH3CH2-,CH2CHCH3CH2-and-CH2CHCH3CH2-)，1.07-0.97(f,3H,-CHCH3CH2-)。
Figure BDA0002794572150000051
In the second step, the transparent liquid polymer poly (4-methyl caprolactone) BDM-PMCL10The preparation method comprises the following steps:
BDM-PMCL10the synthesis process comprises the following steps: all reactants and glass instruments are strictly dewatered, and the reaction process adopts argon protection; 3.23g of 1, 4-Benzenedimethanol (BDM) and 30.00g of 4-methylhexanolide (BDM: MeCL molar ratio ═ 1: 10) prepared in the first step were mixed in a reaction flask, and 0.5 wt% of Sn (Oct) based on the mass of 4-methylhexanolide prepared in the first step was added2Carrying out polymerization reaction for 24 hours at 130 ℃; finally, dissolving the mixture by a little dichloromethane, settling the mixture by petroleum ether, and drying the mixture in vacuum to obtain the transparent liquid polymer BDM-PMCL10(yield 95%). FIG. 2 is a drawing illustrating a second step of preparing BDM-PMCL in biodegradable transparent liquid polyester which can be rapidly photo-cured with mercapto crosslinking agent prepared in example 1 of the present invention1H NMR spectrum.1H NMR(400MHz,CDCl3,TMS):δ＝7.28ppm(s,4H,-C6H4-),5.04(s,1H,-C6H4CH2-),4.03(m,2H,-CH2CH2O-),2.40-2.14(m,2H,-CH2COO-),1.85-1.26(m,5H,-CH2CH2CHCH3-,-CH2CHCH3CH2-,-CHCH3CH2CH2),0.95(s,3H,-CHCH3CH2-). Where x + y is equal to the degree of polymerization 10, and theoretically x-y-5.
Figure BDA0002794572150000052
Figure BDA0002794572150000061
And step three, reacting the product obtained in the step two with Carbonyl Diimidazole (CDI) under the catalysis of potassium hydroxide to obtain transparent liquid BDM-PMCL-CDI, and comprising the following steps:
25.00g of BDM-PMCL obtained in the second step were taken10Dissolving in 500mL of toluene, adding 11.43g N N-carbonyldiimidazole CDI and 1.25g of potassium hydroxide respectively for dissolution, and stirring for reaction at 60 ℃ for 24 hours; after the reaction is finished, washing the mixture by deionized water until two phases are clear; evaporating the lower layer oil phase by rotary evaporation to obtain at least residual liquid, and finally settling and vacuum drying in petroleum ether to obtain transparent liquid BDM-PMCL10CDI (yield 85%). FIG. 3 is a drawing illustrating BDM-PMCL-CDI prepared in the third step of biodegradable transparent liquid polyester capable of being rapidly photo-cured with mercapto crosslinking agent prepared in example 1 of the present invention1H NMR spectrum. x + y is 10, and theoretically x is 5.1H NMR(400MHz,CDCl3,TMS):δ＝8.17ppm,(s,1H,-NCH＝N-),7.39,(s,1H,-NCHCH＝),7.28(s,4H,-C6H4-),7.05(s,1H,-CH＝CHN-),5.04(s,1H,-C6H4CH2-),4.03(m,2H,-CH2CH2O-),2.40-2.14(m,2H,-CH2COO-),1.85-1.26(m,5H,-CH2CH2CHCH3-,-CH2CHCH3CH2-,-CHCH3CH2CH2),0.95(s,3H,-CHCH3CH2-)。
Figure BDA0002794572150000062
Fourthly, reacting the transparent liquid BDM-PMCL-CDI prepared in the third step with 3-butyn-1-ol under the catalysis of potassium hydroxide to obtain transparent liquid poly (4-methyl caprolactone) BDM-PMCL-yne with an alkynyl end group, wherein the method comprises the following steps:
taking 20.00g of transparent liquid BDM-PMCL prepared in the third step10CDI was dissolved in 500mL of toluene, and 2.63g of 3-butyne-1-Dissolving alcohol and 1.00g potassium hydroxide, and stirring and reacting for 24 hours at 60 ℃; after the reaction is finished, washing the mixture by deionized water until two phases are clear; evaporating the lower layer oil phase by rotary evaporation to obtain at least a residual liquid, settling in petroleum ether, and vacuum drying to obtain transparent liquid polyester BDM-PMCL10-yne (yield 90%). FIG. 4 is a drawing illustrating BDM-PMCL-yne prepared in the fourth step of the biodegradable transparent liquid polyester prepared by the invention in example 1 and capable of being rapidly photo-cured with mercapto crosslinking agent1H NMR spectrum.1H NMR(400MHz,CDCl3,TMS):δ＝7.28ppm(s,4H,-C6H4-),5.04(s,1H,-C6H4CH2-),4.18-4.07(m,-OOCCH2CH2-),4.03(m,2H,-CH2CH2O-),2.54-2.42(m,2H,-CH2CH2C-),2.40-2.14(m,2H,-CH2COO-),1.97-1.92(m,1H,-CH2CCH),1.85-1.26(m,5H,-CH2CH2CHCH3-,-CH2CHCH3CH2-,-CHCH3CH2CH2),0.95(s,3H,-CHCH3CH2-). Where x + y is equal to the degree of polymerization 10, and theoretically x-y-5.
Figure BDA0002794572150000071
FIG. 5 is a GPC chart of biodegradable transparent liquid polyester rapidly photo-curable with thiol crosslinking agent prepared in example 1 of the present invention. According to GPC spectrogram, the BDM-PMCL, BDM-PMCL-CDI and BDM-PMCL-yne polymers all have a normal distribution single peak and a polydisperse coefficient
Figure BDA0002794572150000072
All are between 1.20 and 1.30, indicating that the three polymers are stable and uniform. The increasing molecular weight after end group modification is also demonstrated by the increasingly shorter residence times of the three polymers.
FIG. 6 is a schematic view of a rheological test of a biodegradable transparent liquid polyester that can be rapidly photo-cured with a thiol crosslinking agent, prepared in example 1 of the present invention. The rheological test is the change curve of the polymer viscosity with temperature, and it can be seen from fig. 6 that the viscosity of the material is 1-2Pa · s at room temperature, the material is low-viscosity and flowable, and the viscosity is continuously reduced along with the temperature rise, so that the material can be rapidly cured and formed without solvent in the subsequent curing process. Fig. 7 is a schematic view of rapid curing of a transparent polyester photocuring mixture composed of biodegradable transparent liquid polyester prepared in example 1 of the present invention. The transparent polyester light-cured mixed solution is cured and molded for 30-60s under the irradiation of a light source with the wavelength of 405 nm.
FIG. 8 is a schematic view of FT-IR spectrum of a transparent polyester photocuring mixture composed of biodegradable transparent liquid polyester prepared in example 1 of the present invention cured in air. The wave number in the infrared spectrum is 3300cm-1The characteristic peak of the carbon-carbon triple bond on the left and the right disappears completely after the illumination for 30s, and the infrared spectrum is hardly changed after the illumination time is increased to 600s, so that the material is completely cured within 30 s.
Fig. 9 is a schematic view of a cured transparent film of a transparent polyester photocuring mixture composed of biodegradable transparent liquid polyester prepared in example 1 of the present invention. The cured film exhibited good light transmission and flexibility.
Example 2
A method for preparing biodegradable transparent liquid polyester capable of being rapidly photocured with mercapto crosslinking agent comprises the following steps:
step one, 4-methylcyclohexanone is used as a raw material, 3-chloroperoxybenzoic acid is oxidized to obtain transparent liquid monomer 4-methylhexalactone:
dissolving 60.00g of 4-methylcyclohexanone in 100ml of dichloromethane, dropwise adding the solution into 500ml of dichloromethane solution containing 120.00g of 3-chloroperoxybenzoic acid at a constant speed in an ice water bath, reacting at room temperature for 24 hours after the dropwise adding is finished, removing solids by suction filtration, washing the solution by saturated sodium thiosulfate, sodium bicarbonate and sodium chloride aqueous solution in sequence, and distilling under reduced pressure to obtain a transparent liquid monomer 4-methylhexalactone (MeCL).
In the second step, the transparent liquid polymer poly (4-methyl caprolactone) BDM-PMCL50The preparation method comprises the following steps:
BDM-PMCL50the synthesis process comprises the following steps: all reactants and glass instruments are strictly dewatered, and the reaction process adopts argon protection; 0.65g of 1, 4-Benzenedimethanol (BDM) and 30.00g of 4-methylhexanolide (BDM: MeCL molar ratio ═ 1: 50) prepared in the first step were mixed in a reaction flask, and Sn (Oct) was added in an amount of 0.5% by weight based on the 4-methylhexanolide prepared in the first step2Carrying out polymerization reaction for 24 hours at 130 ℃; finally, dissolving the mixture by a little dichloromethane, settling the mixture by petroleum ether, and drying the mixture in vacuum to obtain the transparent liquid polymer BDM-PMCL50(yield 95%).1H NMR(400MHz,CDCl3,TMS):δ＝7.28ppm(s,4H,-C6H4-),5.04(s,1H,-C6H4CH2-),4.03(m,2H,-CH2CH2O-),2.40-2.14(m,2H,-CH2COO-),1.85-1.26(m,5H,-CH2CH2CHCH3-,-CH2CHCH3CH2-,-CHCH3CH2CH2),0.95(s,3H,-CHCH3CH2-). Where x + y is equal to the degree of polymerization 50, theoretically x-y-25.
And step three, reacting the product obtained in the step two with Carbonyl Diimidazole (CDI) under the catalysis of potassium hydroxide to obtain transparent liquid BDM-PMCL-CDI, and comprising the following steps:
25.00g of BDM-PMCL obtained in the second step were taken50Dissolving in 500mL of toluene, adding 2.49g of CDI and 1.25g of potassium hydroxide respectively for dissolving, and stirring and reacting at 60 ℃ for 24 hours; after the reaction is finished, washing the mixture by deionized water until two phases are clear; evaporating the lower layer oil phase by rotary evaporation to obtain at least residual liquid, and finally settling and vacuum drying in petroleum ether to obtain transparent liquid BDM-PMCL50CDI (80% yield).1H NMR(400MHz,CDCl3,TMS):δ＝8.17ppm,(s,1H,-NCH＝N-),7.39,(s,1H,-NCHCH＝),7.28(s,4H,-C6H4-),7.05(s,1H,-CH＝CHN-),5.04(s,1H,-C6H4CH2-),4.03(m,2H,-CH2CH2O-),2.40-2.14(m,2H,-CH2COO-),1.85-1.26(m,5H,-CH2CH2CHCH3-,-CH2CHCH3CH2-,-CHCH3CH2CH2),0.95(s,3H,-CHCH3CH2-). Where x + y is equal to the degree of polymerization 50, theoretically x-y-25.
Fourthly, reacting the transparent liquid BDM-PMCL-CDI prepared in the third step with 3-butyn-1-ol under the catalysis of potassium hydroxide to obtain transparent liquid poly (4-methyl caprolactone) BDM-PMCL-yne with an alkynyl end group, wherein the method comprises the following steps:
taking 20.00g of transparent liquid BDM-PMCL prepared in the third step50Dissolving CDI in 500mL of toluene, adding 3-butyn-1-ol 0.63g and potassium hydroxide 1.00g respectively, dissolving, and reacting under stirring at 60 deg.C for 24 h; after the reaction is finished, washing the mixture by deionized water until two phases are clear; evaporating the lower layer oil phase by rotary evaporation to obtain at least a residual liquid, settling in petroleum ether, and vacuum drying to obtain transparent liquid polyester BDM-PMCL50-yne (85% yield).1H NMR(400MHz,CDCl3,TMS):δ＝7.28ppm(s,4H,-C6H4-),5.04(s,1H,-C6H4CH2-),4.18-4.07(m,-OOCCH2CH2-),4.03(m,2H,-CH2CH2O-),2.54-2.42(m,2H,-CH2CH2C-),2.40-2.14(m,2H,-CH2COO-),1.97-1.92(m,1H,-CH2CCH),1.85-1.26(m,5H,-CH2CH2CHCH3-,-CH2CHCH3CH2-,-CHCH3CH2CH2),0.95(s,3H,-CHCH3CH2-). Where x + y is equal to the degree of polymerization 50, theoretically x-y-25.
Example 3
A method for preparing biodegradable transparent liquid polyester capable of being rapidly photocured with mercapto crosslinking agent comprises the following steps:
step one, 4-methylcyclohexanone is used as a raw material, 3-chloroperoxybenzoic acid is oxidized to obtain transparent liquid monomer 4-methylhexalactone:
dissolving 60.00g of 4-methylcyclohexanone in 100ml of dichloromethane, dropwise adding the solution into 500ml of dichloromethane solution containing 120.00g of 3-chloroperoxybenzoic acid at a constant speed in an ice water bath, reacting at room temperature for 24 hours after the dropwise adding is finished, removing solids by suction filtration, washing the solution by saturated sodium thiosulfate, sodium bicarbonate and sodium chloride aqueous solution in sequence, and distilling under reduced pressure to obtain a transparent liquid monomer 4-methylhexalactone (MeCL).
In the second step, the transparent liquid polymer poly (4-methyl caprolactone) BDM-PMCL100The preparation method comprises the following steps:
BDM-PMCL100the synthesis process comprises the following steps: all reactants and glass instruments are strictly dewatered, and the reaction process adopts argon protection; 0.32g of 1, 4-Benzenedimethanol (BDM) and 30.00g of 4-methylhexanolide (BDM: MeCL molar ratio 1: 100) prepared in the first step were mixed in a reaction flask, and Sn (Oct) was added in an amount of 0.5% by weight based on the 4-methylhexanolide prepared in the first step2Carrying out polymerization reaction for 24 hours at 130 ℃; finally, dissolving the mixture by a little dichloromethane, settling the mixture by petroleum ether, and drying the mixture in vacuum to obtain the transparent liquid polymer BDM-PMCL100(yield 95%).1H NMR(400MHz,CDCl3,TMS):δ＝7.28ppm(s,4H,-C6H4-),5.04(s,1H,-C6H4CH2-),4.03(m,2H,-CH2CH2O-),2.40-2.14(m,2H,-CH2COO-),1.85-1.26(m,5H,-CH2CH2CHCH3-,-CH2CHCH3CH2-,-CHCH3CH2CH2),0.95(s,3H,-CHCH3CH2-). Where x + y is equal to the degree of polymerization 100, and theoretically x-y-50.
And step three, reacting the product obtained in the step two with Carbonyl Diimidazole (CDI) under the catalysis of potassium hydroxide to obtain transparent liquid BDM-PMCL-CDI, and comprising the following steps:
25.00g of BDM-PMCL obtained in the second step were taken100Dissolving in 500mL of toluene, adding 1.26g of CDI and 1.25g of potassium hydroxide respectively for dissolving, and stirring and reacting at 60 ℃ for 24 hours; after the reaction is finished, washing the mixture by deionized water until two phases are clear; evaporating the lower layer oil phase by rotary evaporation to obtain at least residual liquid, and finally settling and vacuum drying in petroleum ether to obtain transparent liquid BDM-PMCL100CDI (80% yield).1H NMR(400MHz,CDCl3,TMS):δ＝8.17ppm,(s,1H,-NCH＝N-),7.39,(s,1H,-NCHCH＝),7.28(s,4H,-C6H4-),7.05(s,1H,-CH＝CHN-),5.04(s,1H,-C6H4CH2-),4.03(m,2H,-CH2CH2O-),2.40-2.14(m,2H,-CH2COO-),1.85-1.26(m,5H,-CH2CH2CHCH3-,-CH2CHCH3CH2-,-CHCH3CH2CH2),0.95(s,3H,-CHCH3CH2-). Where x + y is equal to the degree of polymerization 100, and theoretically x-y-50.
Fourthly, reacting the transparent liquid BDM-PMCL-CDI prepared in the third step with 3-butyn-1-ol under the catalysis of potassium hydroxide to obtain transparent liquid poly (4-methyl caprolactone) BDM-PMCL-yne with an alkynyl end group, wherein the method comprises the following steps:
taking 20.00g of transparent liquid BDM-PMCL prepared in the third step100Dissolving CDI in 500mL of toluene, adding 3-butyn-1-ol 0.32g and potassium hydroxide 1.00g respectively, dissolving, and reacting under stirring at 60 deg.C for 24 h; after the reaction is finished, washing the mixture by deionized water until two phases are clear; evaporating the lower layer oil phase by rotary evaporation to obtain at least a residual liquid, settling in petroleum ether, and vacuum drying to obtain transparent liquid polyester BDM-PMCL100-yne (85% yield).1H NMR(400MHz,CDCl3,TMS):δ＝7.28ppm(s,4H,-C6H4-),5.04(s,1H,-C6H4CH2-),4.18-4.07(m,-OOCCH2CH2-),4.03(m,2H,-CH2CH2O-),2.54-2.42(m,2H,-CH2CH2C-),2.40-2.14(m,2H,-CH2COO-),1.97-1.92(m,1H,-CH2CCH),1.85-1.26(m,5H,-CH2CH2CHCH3-,-CH2CHCH3CH2-,-CHCH3CH2CH2),0.95(s,3H,-CHCH3CH2-). Where x + y is equal to the degree of polymerization 100, and theoretically x-y-50.
Example 4
The embodiment relates to the research of the photocuring rate of a transparent polyester photocuring mixed solution consisting of biodegradable transparent liquid polyester with different polymerization degrees and capable of being rapidly photocured with a mercapto crosslinking agent, and the method specifically comprises the following steps:
Figure BDA0002794572150000101
10.00g of the transparent liquid poly (4-methylhexalactone) BDM-PMCL prepared in example 1 are taken10And (3) uniformly mixing the-yne with 3.06g of pentaerythritol tetra (3-mercaptopropionate) as a crosslinking agent and 0.40g of a photoinitiator TPO-L through ultrasonic oscillation to obtain a transparent polyester photocuring mixed solution, irradiating for 5min by using 405nm light, and observing the curing condition at a specific illumination time point respectively to finally obtain the transparent polyester elastomer.
10.00g of the transparent liquid poly (4-methylhexalactone) BDM-PMCL prepared in example 2 are taken10Uniformly mixing-yne, 0.73g of a cross-linking agent pentaerythritol tetra (3-mercaptopropionate) and 0.32g of a photoinitiator TPO-L through ultrasonic oscillation to obtain a transparent polyester photocuring mixed solution, irradiating for 5min by using 405nm light, and observing the curing condition at a specific illumination time point respectively to finally obtain the transparent polyester elastomer.
10.00g of the transparent liquid poly (4-methylhexalactone) BDM-PMCL prepared in example 3 are taken10Uniformly mixing-yne, 0.37g of pentaerythritol tetra (3-mercaptopropionate) as a cross-linking agent and 0.31g of a photoinitiator TPO-L through ultrasonic oscillation to obtain a transparent polyester photocuring mixed solution, irradiating for 5min by using 405nm light, and observing the curing condition at a specific illumination time point respectively to finally obtain the transparent polyester elastomer.
Table 1 shows the curing conditions of the transparent polyester photocuring mixture composed of biodegradable transparent liquid polyesters with different polymerization degrees prepared in example 4 of the present invention. It can be seen that the photocuring rate of the transparent liquid prepolymer with the polymerization degree of 10 is 30s at the fastest, and the ratio is taken as the optimal polymerization degree ratio for subsequent research.
TABLE 1
10s 20s 30s 40s 50s 60s 70s 80s 90s
x+y＝10 In a viscoelastic state In a viscoelastic state Solid elastic state Solid elastic state Solid elastic state Solid elastic state Solid elastic state Solid elastic state Solid elastic state
x+y＝50 Viscous state Viscous state Viscose body In a viscoelastic state In a viscoelastic state Solid elastic state Solid elastic state Solid elastic state Solid elastic state
x+y＝100 Viscous state Viscous state Viscous state Viscous state Viscose body In a viscoelastic state In a viscoelastic state In a viscoelastic state Solid elastic state
Comparative example 1
This comparative example relates to the selection of the photoinitiator type of the transparent liquid polyester, and the specific procedure is as follows:
transparent liquid polyester BDM-PMCL prepared in example 110-yne, mixing with a cross-linking agent (pentaerythritol tetrakis (3-mercaptopropionate)) and a photoinitiator (benzoin dimethyl ether, DMPA) to obtain a transparent polyester photocuring mixed solution, curing and forming after 365nm illumination, and testing the cross-linking degree of the polyester after a certain illumination time; the method comprises the following steps:
10.00g of the transparent liquid poly (4-methylhexalactone) BDM-PMCL prepared in example 1 are taken10-yne and 3.06g of pentaerythritol tetra (3-mercaptopropionate) as a crosslinking agent are uniformly mixed, 0.13g of DMPA is weighed, dissolved by a small amount of dichloromethane and then added into the mixture to be uniformly mixed by shaking, a small amount of solvent is completely pumped in a vacuum drying oven to obtain a transparent polyester photocuring mixed solution, the transparent polyester photocuring mixed solution is added into a mold by a dropper or a liquid transfer gun, the mold is irradiated by 365nm light for 5min, and the curing conditions are respectively observed at specific time points of the light irradiation.
Comparative example 2
This comparative example relates to the selection of the photoinitiator type of the transparent liquid polyester, and the specific procedure is as follows:
transparent liquid polyester BDM-PMCL prepared in example 110-yne, with crosslinker (pentaerythritol tetrakis (3-mercaptopropionate)), photoinitiator (2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl [)]-1-acetone, Irgacure2959) to obtain a transparent polyester photocuring mixed solution, curing and forming after 365nm illumination, and testing the degree of crosslinking of the polyester after a certain illumination time; the method comprises the following steps:
10.00g of the transparent liquid poly (4-methylhexalactone) BDM-PMCL prepared in example 1 are taken10-yne and 3.06g of pentaerythritol tetra (3-mercaptopropionate) as a crosslinking agent are uniformly mixed, 0.13g of Irgacure2959 is weighed, dissolved by a small amount of dichloromethane and then added into the mixture to be uniformly mixed by shaking, a small amount of solvent is completely pumped in a vacuum drying oven to obtain a transparent polyester photocuring mixed solution, the transparent polyester photocuring mixed solution is added into a mold by a dropper or a pipetting gun, the mold is irradiated by 365nm light for 5min, and the curing conditions are respectively observed at specific time points of illumination.
Example 5
The selection of the photoinitiator type of the transparent liquid polyester comprises the following specific operations:
transparent liquid polyester BDM-PMCL prepared in example 110-yne, mixing with a cross-linking agent (pentaerythritol tetrakis (3-mercaptopropionate)), a photoinitiator ( ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, TPO-L) to obtain a transparent polyester photocuring mixed solution, performing curing molding after 405nm illumination, and testing the cross-linking degree of the prepolymer after a certain illumination time; the method comprises the following steps:
10.00g of the transparent liquid poly (4-methylhexalactone) BDM-PMCL prepared in example 1 are taken10Uniformly mixing the-yne, 3.06g of a cross-linking agent of pentaerythritol tetra (3-mercaptopropionate) and 0.13g of TPO-L to obtain a transparent polyester photocuring mixed solution, adding the transparent polyester photocuring mixed solution into a mold by using a dropper or a pipette, irradiating for 5min by using 405nm light, and observing the curing condition at a specific time point by using the light respectively to obtain a transparent polyester elastomer.
The results of the curing of comparative examples 1, 2 and example 5 are shown in Table 2, and it can be seen that TPO-L has better curing effect than both photoinitiators of comparative examples 1 and 2, and therefore TPO-L was selected as the system photoinitiator.
TABLE 2
Figure BDA0002794572150000121
Example 6
The method relates to the selection of the dosage of a photoinitiator of transparent liquid polyester, and comprises the following specific operations:
transparent liquid polyester BDM-PMCL prepared in example 110-yne, mixing with a cross-linking agent (pentaerythritol tetrakis (3-mercaptopropionate)), a photoinitiator ( ethyl 2,4, 6-trimethylbenzoylphenylphosphonate, TPO-L) (adding 1 wt%, 2 wt%, 3 wt%, 4 wt% four proportions respectively) to obtain a transparent polyester photocuring mixed solution, performing curing molding by 405nm illumination, and testing the cross-linking degree of prepolymers with four photoinitiator proportions after a certain illumination time; the method comprises the following steps:
10.00g of the transparent liquid poly (4-methylhexalactone) BDM-PMCL prepared in example 1 are taken10Uniformly mixing-yne and 3.06g of cross-linking agent pentaerythritol tetra (3-mercaptopropionate) ester with 0.13g, 0.26g, 0.39g and 0.52g of TPO-L respectively through ultrasonic oscillation to obtain a transparent polyester photocuring mixed solution, adding the transparent polyester photocuring mixed solution into a mold through a dropper or a liquid-transferring gun, irradiating for 5min through light with 405nm, observing the curing condition at a specific time point through light respectively, and finally obtaining the transparent polyester elastomer.
The specific curing effect is shown in table 3. It can be seen that the curing rate of the prepolymer can be significantly increased by increasing the amount of the photoinitiator TPO-L from 1% to 3%, while the curing is completed within 30s at 4% without much difference from 3%, so that 3% of the amount of the photoinitiator is finally used.
TABLE 3
5s 10s 15s 20s 30s 40s 50s 60s
TPO-L(1％) Liquid state Viscous state Viscous state Viscose body In a viscoelastic state In a viscoelastic state In a viscoelastic state Solid elastic state
TPO-L(2％) Viscous state Viscous state Viscose body In a viscoelastic state In a viscoelastic state In a viscoelastic state Solid elastic state Solid elastic state
TPO-L(3％) Viscous state In a viscoelastic state In a viscoelastic state In a viscoelastic state Solid elastic state Solid elastic state Solid elastic state Solid elastic state
TPO-L(4％) Viscous state In a viscoelastic state In a viscoelastic state In a viscoelastic state Solid elastic state Solid elastic state Solid elastic state Solid elastic state
Example 7
The embodiment relates to 3D printing and forming of transparent polyester photocuring mixed liquid, and the specific operation and result are as follows:
a transparent polyester photocuring mixed solution (10.00 g of the transparent liquid poly (4-methyl caprolactone) BDM-PMCL prepared in example 1) consisting of biodegradable transparent liquid polyester which can be rapidly photocured with a mercapto crosslinking agent and is prepared in example 110And (3) uniformly mixing the-yne with 3.06g of a cross-linking agent pentaerythritol tetra (3-mercaptopropionate) and 0.40g of a photoinitiator TPO-L through ultrasonic oscillation to obtain a transparent polyester photocuring mixed solution, and performing 3D printing by using a DLP (digital light processing) type 3D printer (ANYCUBIC Photon S). And (3) establishing a three-dimensional model by using 3D max software, carrying out two-dimensional slicing (stored in an STL format) on the model by using slicing software, wherein the number of slicing layers is 20, and the thickness of each layer is 0.05mm, and importing the sliced software into a 3D printer. Pouring 50.000g of transparent polyester photocuring mixed solutionAnd (5) entering a resin tank below, starting a machine, and finishing 3D printing at room temperature. The printed object is shown in fig. 10. Fig. 10 is a schematic 3D printing diagram of a transparent polyester photocuring mixture composed of biodegradable transparent liquid polyester prepared in example 1 of the present invention. The three-dimensional manufacturing of the specific model can be carried out by using a DLP or SLA type liquid resin 3D printer, and the rapid light curing characteristic of the polyester can realize light curing 3D printing.
Example 8
The embodiment relates to an in-vitro degradation test of a transparent polyester elastomer prepared by curing a transparent polyester photocuring mixed solution consisting of biodegradable transparent liquid polyester, and the specific operation and result are as follows:
the biodegradable transparent liquid polyester prepared in example 1, which can be rapidly photo-cured with thiol crosslinking agent, was cured according to the method of example 4, the prepared transparent polyester elastomer was cut into 10 × 5 × 2 mM-sized sample strips, added to 20mM PBS buffer solution (pH 7.0) containing 20U/ml lipase, and then placed in a constant temperature shaking incubator at 37 ℃ and a shaking rate of 80r/min, and after different time intervals of incubation, the remaining crosslinked polymer was taken out, dried and weighed. All samples were run in 3 replicates and the results are expressed as mean ± sd. The specific degradation results are shown in FIG. 11. FIG. 11 is a graph showing the in vitro degradation curve of the elastomer cured by the light-cured transparent polyester mixed solution composed of the biodegradable transparent liquid polyester prepared in example 1 of the present invention. About 22% of the mass can be degraded in 72 hours, which indicates that the material has biodegradability.
Example 9
This example relates to a cell proliferation experiment of a transparent polyester elastomer prepared by curing a transparent polyester photocuring mixed solution composed of biodegradable transparent liquid polyester prepared in example 1, and the specific operations and results are as follows:
the biodegradable transparent liquid polyester prepared in example 1, which can be rapidly photo-cured with thiol crosslinking agent, was cured according to the method of example 4, and the prepared transparent polyester elastomer was cut into discs having a size of 8mm in diameter and 1mm in thickness, respectively, and placed in a 24-well TCPS by cutting at room temperature in the form of a waferSoaking in 75% ethanol for 24 hr for sterilization, washing with PBS for three times, and mixing with 2 × 10 cell suspension of Mesenchymal Stem Cells (MSC)4The density of individual cells/well was seeded on the material, maintained at 37 ℃ and 5% CO2And culturing in a humid atmosphere. At certain time points, cells were counted by the CCK-8 method, and the corresponding OD values were measured, all data in triplicate, and the results were expressed as mean. + -. Standard Deviation (SD). Fig. 12 shows the cell proliferation results, and fig. 12 is a schematic view of the cell proliferation of the elastomer after the transparent polyester photocuring mixed liquid composed of the biodegradable transparent liquid polyester prepared in example 1 of the present invention is cured. When the mesenchymal stem cells are inoculated on the solidified polyester material, the cell proliferation amount of 7 days can reach about 70 percent, which indicates that the material has good cell compatibility.
Although the present invention has been described with reference to a preferred embodiment, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (7)

1. A biodegradable transparent liquid polyester capable of being rapidly photocured with a mercapto crosslinking agent is characterized by having the following structure:
Figure FDA0002794572140000011
x + y is 10 to 100, and theoretically x ═ y.
2. The biodegradable transparent liquid polyester capable of being rapidly photo-cured with thiol crosslinking agent according to claim 1, characterized in that x + y is 10, theoretically x-y is 5; or x + y is 50, theoretically x is 25; or x + y 100, theoretically x y 50.
3. A method for preparing biodegradable transparent liquid polyester capable of being rapidly photo-cured with thiol crosslinking agent according to claim 1 or 2, comprising the steps of:
the preparation method of the transparent liquid monomer 4-methyl caprolactone comprises the following steps:
dropwise adding a dichloromethane solution of 4-methylcyclohexanone into a dichloromethane solution of 3-chloroperoxybenzoic acid at a constant speed in an ice water bath, wherein the mass ratio of 4-methylcyclohexanone to 3-chloroperoxybenzoic acid is 1 (1.5-4), and reacting at room temperature for 1-24 h after dropwise adding is finished to obtain a transparent liquid monomer 4-methylhexanolide;
in the second step, the preparation method of the transparent liquid polymer poly (4-methyl caprolactone) BDM-PMCL comprises the following steps:
under the protection of argon and under the anhydrous condition, 1, 4-benzenedimethanol with the molar ratio of 1 (10-200) and 4-methyl caprolactone prepared in the first step are uniformly mixed, and Sn (Oct) accounting for 0.5 wt% of the mass of the 4-methyl caprolactone prepared in the first step is added2Carrying out polymerization reaction for 1-24 h at the temperature of 120-140 ℃ to obtain a transparent liquid polymer poly (4-methyl caprolactone) BDM-PMCL;
thirdly, the preparation method of the transparent liquid BDM-PMCL-CDI comprises the following steps:
dissolving the transparent liquid polymer BDM-PMCL obtained in the second step into toluene, then respectively adding CDI and potassium hydroxide, wherein the mass ratio of the BDM-PMCL to the CDI to the potassium hydroxide is 20 (0.4-10): 1, and reacting for 1-24 h at the temperature of 50-70 ℃ to obtain the transparent liquid BDM-PMCL-CDI;
fourthly, the preparation method of the transparent liquid poly (4-methyl caprolactone) BDM-PMCL-yne with the end group of alkynyl comprises the following steps:
and (3) dissolving the transparent liquid BDM-PMCL-CDI prepared in the third step in toluene, adding 3-butine-1-alcohol and potassium hydroxide respectively for dissolving, wherein the mass ratio of the BDM-PMCL-CDI to the 3-butine-1-alcohol to the potassium hydroxide is 20 (0.1-3): 1, and reacting for 1-24 hours at the temperature of 50-70 ℃ to obtain the transparent liquid polyester BDM-PMCL-yne.
4. A transparent polyester photocuring mixture prepared from the biodegradable transparent liquid polyester which can be rapidly photocured with a mercapto crosslinking agent according to claim 1 or 2, which is characterized by being prepared from the following components: biodegradable transparent liquid polyester, a cross-linking agent containing sulfydryl and a photoinitiator; the mass ratio of the biodegradable transparent liquid polyester to the crosslinking agent containing sulfydryl is 10 (0.1-5), and the photoinitiator accounts for 1-3% of the total mass of the biodegradable transparent liquid polyester, the crosslinking agent containing sulfydryl and the photoinitiator.
5. The transparent polyester mixed light curing solution as claimed in claim 4, wherein the crosslinking agent containing a mercapto group is pentaerythritol tetrakis (3-mercaptopropionate).
6. The mixed liquid for photocuring transparent polyester as claimed in claim 4, wherein the photoinitiator is ethyl 2,4, 6-trimethylbenzoylphenylphosphonate.
7. The method for preparing the transparent polyester photocuring mixture according to any one of claims 4 to 6, comprising the steps of:
and (2) carrying out ultrasonic oscillation and uniform mixing on the transparent liquid polyester, a cross-linking agent containing sulfydryl and a photoinitiator to obtain a transparent polyester photocuring mixed solution, and irradiating for 30 s-5 min by using 405nm light to obtain the transparent polyester elastomer.
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